Alkylation of heme by the antimalarial drug artemisinin

The peroxide function of artemisinin has been activated by iron(II)-heme generated in situ from iron(III)-protoporphyrin-IX and glutathione, a biologically relevant reductant. In mild conditions, this reaction produced a high yield (85%) of heme derivatives alkylated at alpha-, beta-, and delta-meso positions by a C4-centered radical derived from artemisinin.     

Polymerization by transition metal derivatives. XII. Factors controlling activity and stereospecificity in the 1,4 polymerization of butadiene by monometallic nickel catalysts

In the course of investigations of polymerization of diolefins by transition metal derivatives, we have synthesized various monometallic nickel coordination catalysts. The complexes were prepared by reacting 2,6,10-dodecatriene-1,12-diyl nickel with protonic acids; they were shown to initiate the stereospecific polymerization of 1,3-butadiene. The study of these catalysts showed the strong influence of the nature of the counteranion used on the stereospecificity and the polymerization rate. Moreover, by adding various ligands, we were able to modify the behavior of the catalytic systems and to prepare either pure cis-1,4 or pure trans-1,4 or cis–trans equibinary polybutadienes, starting from the same complex and keeping a high 1,4 specificity. Some of these modifications were shown to be reversible.     

Extended average energy perturbation calculation of the 2s2 and 2p21S resonance state energies of two-electron atoms

An extended average energy (EAE) calculation of the 2s² and 2p²¹S resonance state energies of two-electron atoms is carried out. We take the bare-nucleus hamiltonian as the initial approximation and treat the zeroth-order degeneracy by van Vleck perturbation theory, For both H^? and He the lower state energies agree quite well with experiment while the upper state is about 1–2 eV too high. Our remits for He are comparable in accuracy to those obtained by the 1/Z Hartree—Fock perturbation method. A brief concluding discussion of ways to improve the simple EAE technique is presented.     

Thermally stable silarylene-1,3,4-oxadiazole polymers

The effects of incorporating a p-phenylene- (or m-phenylene)-1,3,4-oxadiazole fragment into the backbone of poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)], which was developed by the authors, was investigated. Bis[(p-carbohydrazidophenyl)]diphenylsilane was copolymerized with dipentachlorophenyl terephthalate or isophthalate to produce the prepolymers poly[N-(p-diphenylsilylbenzoyl)-N′N″-(terephthaloyl)-N″′-(p-benzoyl)dihydrazide] and poly[N-(p-diphenylsilylbenzoyl)-N′,-N″-(isophthaloyl)-N″′-p-(benzoyl) dihydrazide], respectively. The polyhydrazides were converted by thermal dehydration into poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)] and poly[1,4-phenyl-ene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,3,4-(oxadiazole)]. The new polymers were soluble in organic solvents. Films cast from these solutions exhibited good adhesion to glass and metal surfaces. Thermal analysis showed that the heat stability of all these polymers was about the same and that they were resistant to decomposition when heated in air to about 400°C. The results also indicated that these polymers were somewhat less heat-resistant than samples of poly-[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-]1,3,4-(oxadiazole) synthesized from bis(p-carbohydrazidophenyl)diphenylsilane and bis-(p-carbopentachlorophenoxy-phenyl)diphenylsilane.     

Concise synthesis of anhydrovinblastine from leurosine

[reaction: see text] The Cp(2)TiCl-mediated deoxygenation of leurosine (1) afforded anhydrovinblastine (4) in good yield. Furthermore, as the reaction proceeded via a carbon-centered radical intermediate, this transient was also trapped by a hydrogen-atom donor to afford selectively reduced alkaloid 10.     

Nature et stabilité des complexes métalliques de cryptands dinucléants en solution II. Polythiamacrotricycles et monocycles apparentés

Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution II. Polythiamacrotricycles and Related Monocyclic Subunits The stability constants of the Cu²⁺ and Ag⁺ complexes of the cylindrical macrotricycle 1a (1,7,13,19-tetraaza 4,16-dioxa 10,22,27,32-tetrathiatricyclo[17.5.5.5]tetratriacontane) have been determined by pH-metry, as well as those of the Cu²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Ag⁺ complexes of the monocyclic subunit 2a (1,7-dimethyl-1,7-diaza 4,10-dithiacyclododecane), in aqueous solutions (NaClO₄) at 25°. In the Cu(II) systems, equilibria were reached slowly, and the results established by pH-metry were confirmed by UV/VIS spectrophotometric studies. The tricycle 1a forms dinuclear cryptates with copper and silver, with overall stability constants log β₂₁₀ (Cu₂- 1a )⁴⁺ = 18.5, log β_21-2 (Cu₂- 1a (OH)₂)²⁺ = 4.8, log β₂₁₀(Ag₂- 1a )²⁺ = 23.0. Ag⁺ also forms a mononuclear (Ag- 1a )⁺ complex, with log β₁₁₀ = 13.1, but no mononuclear species were detected in the Cu- 1a system. The absorption spectra of the bis-Cu(II) complexes of 1a and 2a in aqueous medium, MeOH and propylene carbonate (PC) are given, as well as those, in MeOH and PC, of the bis-copper complexes of the related monocycles 3 and 4 (1,7-diaza-4,10,13-trithiacyclopentadecane and 1.10-diaza 4,7,13,16-tetrathiacyclooctadecane, respectively), and tricycle 5 with two benzyl groups in the lateral chains. The complexing properties of the polyoxa- and polythia macrotricycles (Parts I and II of this series) are compared to those of other bis-chelating ligands, the bicyclic bis-tren and the monocyclic bis-dien.     

Determination de la constante d'acidite intrinseque d'un echangeur d'ions carboxylique

To obtain the intrinsic acidity constant of a carboxylic ion-exchanger, we propose a method of graphical double extrapolation. The results for an ion-exchanger made of polyvinyl alcohol grafted with acrylic acid are close to those published for the corresponding linear polyacid.     

Observation of several phase transitions in tetrachloro-o-benzoquinone using 35Cl nuclear quadrupole resonance

The temperature dependence of the ³⁵Cl nuclear quadrupole resonance spectra of tetrachloro-o-benzoquinone (TOB) is reported. An analysis of the change in line multiplicities suggests that TOB undergoes three phase changes in going from 77 to 330 K. The transition temperatures have been determined.